EP2679544A1 - Sphärische Trimanganesetetroxid mit geringer BET-spezifischen Oberfläche und Verfahren zur Herstellung davon - Google Patents

Sphärische Trimanganesetetroxid mit geringer BET-spezifischen Oberfläche und Verfahren zur Herstellung davon Download PDF

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EP2679544A1
EP2679544A1 EP13171509.6A EP13171509A EP2679544A1 EP 2679544 A1 EP2679544 A1 EP 2679544A1 EP 13171509 A EP13171509 A EP 13171509A EP 2679544 A1 EP2679544 A1 EP 2679544A1
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solution
reaction
filtrate
solid
trimanganese tetroxide
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French (fr)
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Xiaojing Wu
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Shenzhen Xinhaoqing Science and Technology Co Ltd
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Shenzhen Xinhaoqing Science and Technology Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]

Definitions

  • the present invention relates to a method for preparing spherical trimanganese tetroxide with low BET specific surface area, and the spherical trimanganese tetroxide produced by the method.
  • Trimanganese tetroxide raw material is commonly used for preparation of manganese cathode materials for lithium ion secondary battery, which requires the trimanganese tetroxide raw material possess the properties of small specific surface area, low impurity content, spherical particle, pure crystalline phase structure and so on. Recently, with increase of the rate performance requirement for lithium ion secondary battery, there are further requirements for particle size distribution of the trimanganese tetroxide.
  • a method for preparing Mn 3 O 4 by adding aqua ammonia into MnSO 4 /H 2 O solution is disclosed in CN1814551A .
  • the oxidation rate of divalent manganese and the recovery rate of manganese are largely increased, but it can not be ensured to obtain pure phase Mn 3 O 4 , meanwhile, because the physical indexes such as particle size distribution, specific surface area and so on, are not studied and technically controlled during the process for preparing Mn 3 O 4 , the obtained Mn 3 O 4 is not suitable for preparing LMO (lithium manganate) materials.
  • Aqua ammonia is a monobasic weak base, the dissociation constant of which is 1.8 ⁇ 10 -5 .
  • Mixing aqua ammonia with MnSO 4 can obtain a buffer solution, and the pH value of the buffer solution is far less than 14.
  • the inventor confirms that Mn can be oxidized to be Mn 3 O 4 with air or oxygen oxidation only when the pH value is 6.4 ⁇ 7.64, no Mn 3 O 4 will be produced when the pH value is less than 6.4, meanwhile, and a large quanity of Mn(OH) 2 may be produced when pH value is too high.
  • Mn(OH) 2 Because electric potential of oxygen is much higher than electric potential that Mn(OH) 2 is oxidized to Mn 3 O 4 , Mn(OH) 2 will be oxidized to Mn 2 O 3 , which leads to phenomenon of mischcrystal and thus the quality of Mn 3 O 4 is reduced.
  • the patent publication No. 101898796A discloses a method for preparing Mn 3 O 4 with MnSO 4 /H 2 O/NH 4 OH/air system.
  • pH value of MnSO 4 solution with the concentration of 50 ⁇ 120g/L is controlled between 4.5 ⁇ 8.0, and the MnSO 4 solution is directly oxidized with air at 50 ⁇ 80°C to produce Mn 3 O 4 with properties that tap density is1.95 ⁇ 2.25g/cm 3 , BET is 1.9419 ⁇ 2.9015m 2 /g, D 50 is 7.21 ⁇ 10.72 ⁇ m.
  • the technical problem solved by the present invention is overcoming the shortcomings of the prior art, providing a method for preparing spherical high-purity Mn 3 O 4 with D 50 of 4.5 ⁇ 5.5 ⁇ m and BET ⁇ 1.0 m 2 /g.
  • supplementary MnSO 4 is needed to be added for reacting so that the content of Mn may reach 70.5%, the essential reason of which is that technical means of controlling redox potential are lacked, part of Mn 2 O 3 is produced and thus Mn% decreases.
  • MnSO 4 solution with high concentration is utilized in the present invention, so (NH 4 ) 2 SO 4 with higher concentration is generated after reaction and higher ion strength is formed, thus redox potential is stablized, therefore, Mn 3 O 4 with low particle size can be produced, which increase rate charge and discharge performance of battery, at the same time, the content index of Mn in Mn 3 O 4 can be assured.
  • Trimanganese tetroxide obtained in Example 1 of CN101898796A has BET of 1.9419 m 2 /g and D 50 of 8.42 ⁇ m, large internal surface area exists comparing with the theoretical density of 4.50 g/cm 3 , this may be caused by reaction temperature, controlling of reaction rate and small particles agglomerating when of NH 4 OH is added and partial filtratian is carried out.
  • the present invention provides following technical solution to solve the above technical problem existing in the prior art.
  • a method for preparing spherical trimanganese tetroxide characterized in that it comprises following processes:
  • MnS and peroxide are sequentially added to MnSO 4 solution whose concentration is 130 ⁇ 200g/L to remove impurities, and the mixture is neutralized to pH value of 5.0 ⁇ 5.5, and then the mixture is separated by solid-liquid separation to obtain manganese sulfate filtrate;
  • MnS is added to carry out reaction according to the proportion of 2.5 ⁇ 3.0 kg of MnS per cubic meter of solution.
  • process (1) when said peroxide is barium peroxide, barium peroxide is added to the solution according to the proportion of 1.5 ⁇ 2.2 kg per cubic meter of solution and impurities are removed with oxidation reaction under the condition that the mixture is boiling; when said peroxide is hydrogen peroxide, hydrogen peroxide is added to the solution according to 2.5L of 27.5wt% hydrogen peroxide per cubic meter of solution and impurities are removed with oxidation reaction under the condition that the mixture is boiling.
  • the solid is washed with deionized water at a temperature of 70 ⁇ 80°C according to the weight ratio of solid to liquid of :5.
  • drying is maintained for 23 ⁇ 26 hours at a temperature range of 100 ⁇ 110°C, preferably drying is maintained for 24 hours at 105°C.
  • the present invention also provides a spherical trimanganese tetroxide product prepared by the above methods of the present invention.
  • the spherical trimanganese tetroxide product of the present invention has properties that BET specific surface area is less than 1m 2 /g, D 90 is 7.0 ⁇ 8.5 ⁇ m, D 10 is 2.6 ⁇ 3.2 ⁇ m and D 50 is 4.0 ⁇ 5.5 ⁇ m.
  • the spherical trimanganese tetroxide product of the present invention has properties that BET specific surface area is 0.7122 ⁇ 0.8214m 2 /g, D 90 is 7.029 ⁇ 8.456 ⁇ m, D 10 is 2.626 ⁇ 3.139 ⁇ m, D 50 is 4.302 ⁇ 5.185 ⁇ m, D max is 15.138 ⁇ m, bulk density is 2.31 ⁇ 2.64g/cm 3 and Mn% is 71.44 ⁇ 71.08wt%.
  • Chemical reactions involved in the present invention preparation method mainly comprise: 6Mn 2+ +6H 2 O+O 2 ⁇ 2Mn 3 O 4 ⁇ +12H + 6MnSO 4 +6H 2 O+O 2 +12NH 3 ⁇ 2Mn 3 O 4 +6(NH 4 ) 2 SO 4 CaO+(NH 4 ) 2 SO 4 ⁇ CaSO 4 +2NH 3 ⁇ +H 2 O
  • the spherical trimanganese tetroxide product prepared by the methods of the present invention has properties of small particle size, narrow particle size distribution, pure phase, low impurity content, whose BET specific surface area is less than 1m 2 /g.
  • the spherical trimanganese tetroxide product has properties that D 90 is 7.0 ⁇ 8.5 ⁇ m, D 10 is 2.6 ⁇ 3.2 ⁇ m, D 50 is 4.0 ⁇ 5.5 ⁇ m, D max is 15.138 ⁇ m, Mn% is 71.44 ⁇ 71.08wt%, wherein, contents of impurities K, Na, Ca, Mg, Fe, Cu, Zn, Pb, Cd and so on are very low, and particularly, the weight content of K is less than or equal to 8.4ppm, the weight content of Na is less than or equal to 10.6ppm, the weight content of Ca is less than or equal to 27.0ppm, the weight content of Mg is less than 10.0ppm, and the weight content of Fe is less than or equal to 4.7
  • spherical trimanganese tetroxide having properties of low BET specific surface area, small particle size and pure phase is prepared by the following methods in the present invention, characterized in that, the methods comprise following processes:
  • MnS is added to MnSO 4 solution whose concentration is 130 ⁇ 200g/L (preferably according to the proportion of 2.5 ⁇ 3.0 kg of MnS per cubic meter of solution) to carry out reaction (preferably reacting under agitation for 3 ⁇ 4 hours at 90 ⁇ 95°C), so as to convert impurity ions of heavy metals in the solution into insoluble sulfides, and then, the mixture is separated by solid-liquid separation and peroxide is added to the obtained filtrate (the peroxide may be barium peroxide or hydrogen peroxide, barium peroxide is added according to the proportion of 1.5 ⁇ 2.2 kg per cubic meter) to remove impurities with oxidation reaction (preferably keeping the reaction mixture boiling under agitation, more preferably keeping the reaction mixture slightly boiling for 50 ⁇ 60 minutes, in order to remove impurities such as iron and so on), after that, pH value of the mixture is neutralized to pH5.0 ⁇ 5.5 and the mixture is separated by solid-liquid separation and manganese sulfate filtrate is obtained;
  • FIG. 1 is a process flow diagram of the method of the present invention
  • figure 2 is a structure schematic diagram of the reaction device used in the preparation method of the present invention.
  • the method of the present invention for preparing Mn 3 O 4 comprises the following processes:
  • the concentration of MnSO 4 solution is adjusted to 130 ⁇ 200 g/L, and MnS is added to the solution according to the proportion of 2.5 ⁇ 3.0 kg of MnS per cubic meter of solution to carry out reaction under agitation for 3 ⁇ 4 hours at a temperature of 90 ⁇ 95°C, so as to convert impurity ions of heavy metals in the solution into insoluble sulfides, and then, the mixture is separated by pressure-filtration to obtain filter and the filter residue, the filer residue is discarded and pH value of the filtrate is adjusted to 2.5 ⁇ 3.0 with sulfuric acid.
  • Hydrogen peroxide is added according to the proportion of 2.5L of 27.5wt% hydrogen peroxide per cubic meter, the mixture is kept slightly boiling for 50 ⁇ 60 minutes under agitation and whose pH value is adjusted to 5.0 ⁇ 5.5 with 2 mol/L Ba(OH) 2 solution, the mixture is separated by pressure-filtration to obtain the filtrate and filter residue, and the filter residue is discarded.
  • chemical reactions involved in the foregoing pre-treatment process mainly comprise: M+S 2- ⁇ MS (M is a metal ion, may be Zn, Cu, Pb, Cd and so on)
  • the above filtrate obtained in the process (1) is placed at the bottom of reactor 1, and the filtrate is cooled to 25 ⁇ 30°C with pipe coil of the reactor 1.
  • Atmospheric valve 2 is opened, moreover, oxygen valve 10 and ammonia gas valve 11 are opened, and the air in the reactor is replaced with the mixture gas of O 2 -NH 3 , after which the atmospheric valve 2 is closed.
  • valve 7 is opened and recycle pump 6 is turned on, the manganese sulfate filtrate obtained in process (1) is discharged through valve 7 via the bottom of reactor 1 and is sprayed through spray nozzle 3 with the help of recycle pump 6, and the spray liquid reacts with the mixture gas of O 2 -NH 3 introduced into the reactor.
  • reaction temperature is maintained by opening and closing cooling water valve 12 to regulate cooling water so that reading on the thermometer 8 shows the temperature at a range of 25 ⁇ 30°C.
  • Reaction product sample taken via opening for sampling 5 is analyzed and the reaction will not stop until [Mn 2+ ] ⁇ 11.5 g/L in the solution, i.e., if the concentration of Mn 2+ of the solution is [Mn 2+ ]>1.5 g/L by analyzing sample taken via opening for sampling 5 during reaction, the manganese sulfate reaction solution discharged through valve 7 should be sprayed circularly.
  • Chemical reaction involved in the process mainly comprises: CaO+(NH4) 2 SO 4 ⁇ CaSO 4 ⁇ +NH 3 ⁇
  • the concentration of 100 m 3 of MnSO 4 solution was adjusted to 130 g/L, and MnS was added to the solution according to the proportion of 2.5 kg of MnS per cubic meter of solution to carry out reaction under agitation for 3 hours at a temperature of 90°C, so as to convert impurity ions of heavy metals in the solution into insoluble sulfides, and then, the mixture is separated by pressure-filtration to obtain filter and the filer residue, the filter residue was discarded and pH value of the filtrate was adjusted to 2.5 ⁇ 3.0 with sulfuric acid.
  • Hydrogen peroxide was added according to the proportion of 2.5L of 27.5wt% hydrogen peroxide per cubic meter, the mixture was kept slightly boiling for 50 minutes under agitation and whose pH value is adjusted to 5.0 with 2 mol/L Ba(OH) 2 solution , the mixture is pressure-filtration to obtain the filtrate and filter residue, and the filter residue was discarded.
  • the above filtrate obtained in the process (1) was placed at the bottom of reactor 1 and the filtrate is cooled to 25 ⁇ 26°C with pipe coil of the reactor 1, atmospheric valve 2 was opened, moreover, oxygen valve 10 and ammonia gas valve 11 were opened, and the air in the reactor is replaced with the mixture gas of O 2 -NH 3 , after which atmospheric valve 2 was closed.
  • valve 7 was opened and recycle pump 6 was turned on, the manganese sulfate filtrate obtained in process (1) was discharged through valve 7 via the bottom of reactor 1, and was sprayed through spray nozzle 3 with the help of recycle pump 6, and the spray liquid reacted with the mixture gas of O 2 -NH 3 introduced into the reactor.
  • the reaction temperature is maintained by opening and closing cooling water valve 12 to regulate cooling water so that reading on the thermometer 8 showed the temperature at a range of 25 ⁇ 26°C.
  • Reaction product sample taken via opening for sampling 5 was analyzed and the reaction stopped when [Mn 2+ ] ⁇ 1.5 g/L in the solution, during reaction, if the concentration of Mn 2+ of the solution is [Mn 2+ ]> 1.5 g/L in the solution by analyzing sample taken via opening for sampling 5, the manganese sulfate reaction solution discharged through valve 7 should be sprayed circularly.
  • the Mn 3 O 4 product sample doesn't contain any impurity phase, peaks in the XRD diffraction spectrum are narrow and the strength of the peaks are high, which indicates crystal structure of the Mn 3 O 4 product sample is complete, defect existing in the crystal structure is little and impurity phase of manganites is not contained basically.
  • the Mn 3 O 4 product sample is small particle and whose particle size distribution is narrow, and the particular data of particle size distribution is shown in table 1.
  • the concentration of 100 m 3 of MnSO 4 solution was adjusted to 170 g/L, and MnS was added to the solution according to the proportion of 3.0 kg of MnS per cubic meter of solution to carry out reaction under agitation for 4 hours at a temperature of 95°C, so as to convert impurity ions of heavy metals in the solution into insoluble sulfides, and then, the mixture is separated by pressure-filtration to obtain filter and the filer residue, the filter residue was discarded and pH value of the filtrate was adjusted to 2.5 ⁇ 3.0 with sulfuric acid.
  • Hydrogen peroxide was added according to the proportion of 2.5L of 27.5wt% hydrogen peroxide per cubic meter, the mixture was kept slightly boiling for 60 minutes under agitation and whose pH value is adjusted to 5.5 with 2 mol/L Ba(OH) 2 solution, the mixture is separated by pressure-filtration to obtain the filtrate and filter residue, and the filter residue was discarded.
  • the above filtrate obtained in the process (1) was placed at the bottom of reactor 1 and the filtrate is cooled to 27 ⁇ 28°C with pipe coil of the reactor 1, atmospheric valve 2 was opened, moreover, oxygen valve 10 and ammonia gas valve 11 were opened, and the air in the reactor is replace with the mixture gas of O 2 -NH 3 , after which atmospheric valve 2 was closed.
  • valve 7 was opened and recycle pump 6 was turned on, the manganese sulfate filtrate obtained in process (1) was discharged through valve 7 via the bottom of reactor 1, and was sprayed through spray nozzle 3 with help of recycle pump 6, and the spray liquid reacts with the mixture gas of O 2 -NH 3 introduced into the reactor.
  • the reaction temperature is maintained by opening and closing cooling water valve 12 to regulate cooling water so that reading on the thermometer 8 showed the temperature at a range of 27 ⁇ 28°C.
  • Reaction product sample taken via opening for sampling 5 was analyzed and the reaction stopped when [Mn 2+ ] ⁇ 1.5 g/L in the solution, if the concentration of Mn 2+ of the solution is [Mn 2+ ] > 1.5 g/L in the solution by analyzing sample taken via opening for sampling 5 during reaction, the manganese sulfate reaction solution discharged through valve 7 should be sprayed circularly.
  • Mn 3 O 4 product sample 2 # is obtained by drying the solid for 23 hours at 110°C.
  • the particle of Mn 3 O 4 sample is subsphaeroidal and the particle size distribution is uniform.
  • the Mn 3 O 4 product sample is small particle and whose particle size distribution is narrow, and the particular data of particle size distribution is shown in table 1.
  • the concentration of 100 m 3 of MnSO 4 solution was adjusted to 200 g/L, and MnS was added to the solution according to the proportion of 2.8 kg of MnS per cubic meter of solution to carry out reaction under agitation for 4 hours at 93°C, so as to convert impurity ions of heavy metals in the solution into insoluble sulfides, and then, the mixture is separated by pressure-filtration to obtain filter and the filer residue, the filter residue was discarded and pH value of filtrate was adjusted to 2.5 ⁇ 3.0 with sulfuric acid.
  • Hydrogen peroxide was added in according to the proportion of 2.5L of 27.5wt% hydrogen peroxide per cubic meter, the mixture was kept slightly boiling for 55 minutes under agitation and whose pH value is adjusted to 5.3 with 2 mol/L Ba(OH) 2 solution, the mixture is separated by pressure-filtration to obtain the filtrate and filter residue, and filter residue was discarded.
  • the above filtrate obtained in the process (1) was placed at the bottom of reactor 1 and the filtrate is cooled to 28 ⁇ 30°C with pipe coil of the reactor 1, atmospheric valve 2 was opened, moreover, oxygen valve 10 and ammonia gas valve 11 were opened, and the air in the reactor is replaced with the mixture gas of O 2 -NH 3 , after which atmospheric valve 2 was closed.
  • valve 7 was opened and recycle pump 6 was turned on, the manganese sulfate filtrate obtained in process (1) was discharged through valve 7 via the bottom of reactor 1, and was sprayed through spray nozzle 3 with the help of recycle pump 6, and the spray liquid reacted with the mixture gas of O 2 -NH 3 introduced into the reactor.
  • the reaction temperature is maintained by opening and closing cooling water valve 12 to regulate cooling water so that reading on the thermometer 8 showed the temperature at a range of 28 ⁇ 30°C.
  • Reaction product sample taken via opening for sampling 5 was analyzed and the reaction stopped when [Mn 2+ ] ⁇ 1.5 g/L in the solution, during reaction, if the concentration of Mn 2+ of the solution is [Mn 2+ ] > 1.5 g/L in the solution by analyzing sample taken via opening for sampling 5, the manganese sulfate reaction solution discharged through valve 7 should be sprayed circularly.
  • the Mn 3 O 4 product sample doesn't contain any impurity phase, the peaks in the XRD diffraction spectrum are narrow and the strength of the peaks are high, which indicates crystal structure of the Mn 3 O 4 product sample is complete, defect existing in the crystal structure is little and impurity phase of manganites is not contained basically.
  • the Mn 3 O 4 product sample is small particle and whose particle size distribution is narrow, and the particular data of particle size distribution is shown in table 1.
  • Mn% is 71.44-71.08 wt%; besides, contents of impurities are very low, and contents of impurities K, Na, Ca, Mg, Fe, Cu, Zn, Pb and Cd are very low, wherein, content of K is less than or equal to 8.4ppm, content of Na is less than or equal to 10.6ppm, content of Ca is less than or equal to 27.0ppm, content of Mg is less than 10.0ppm, content of Fe is less than or equal to 4.7ppm, specially, contents of Cu, Zn, Pb and Cd are all respectively less than 0.1ppm.
  • particle diameter of Mn 3 0 4 particle is small, BET specific surface area of Mn 3 O 4 particle is low and is less than 1m 2 /g, D 90 of Mn 3 O 4 particle is 7.0 ⁇ 8.5 ⁇ m, D 10 of Mn 3 O 4 particle is 2.6 ⁇ 3.2 ⁇ m, D 50 of Mn 3 O 4 particle is 4.0 ⁇ 5.5 ⁇ m, and D max of Mn 3 O 4 particle is 15.138 ⁇ m.
  • BET specific surface area of samples 1 # ⁇ 3 # is 0.7122 ⁇ 0.8214m 2 /g
  • D 90 of samples 1 # ⁇ 3 # is 7.029 ⁇ 8.456 ⁇ m
  • D 10 of samples 1 # ⁇ 3 # is 2.626 ⁇ 3.139 ⁇ m
  • D 50 of samples 1 # ⁇ 3 # is 4.302 ⁇ 5.185 ⁇ m
  • bulk density of samples 1 # ⁇ 3 # is 2.31 ⁇ 2.64g/cm 3 .
  • Mn 3 O 4 particle prepared by the method of the present invention possess the properties of low impurity content, spherical particle, pure crystalline phase structure, which meets the requirements of manganese cathode materials for high rate charge and discharge performance.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Battery Electrode And Active Subsutance (AREA)
EP13171509.6A 2012-06-26 2013-06-11 Sphärische Trimanganesetetroxid mit geringer BET-spezifischen Oberfläche und Verfahren zur Herstellung davon Withdrawn EP2679544A1 (de)

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EP2679543A3 (de) * 2012-06-26 2016-03-23 Guizhou Redstar Developing Co., Ltd. Verfahren zur Herstellung von Trimangantetroxid mit gering spezifischem BET-Oberflächenbereich, Verfahren zum Steuern der Teilchengröße von Trimangantetroxid und Trimangantetroxidprodukt

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CN113156059B (zh) * 2021-04-20 2023-06-09 中国电子科技集团公司第四十九研究所 一种管状结构纳米锰氧化物材料的制备方法
CN114655987A (zh) * 2021-12-31 2022-06-24 宁夏天元锰材料研究院(有限公司) 一种生产四氧化三锰联产铅银合金的方法
CN115180651A (zh) * 2022-09-09 2022-10-14 河南科隆新能源股份有限公司 一种粒度可控的锰酸锂用四氧化三锰材料的制备方法
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CN119841353B (zh) * 2025-01-02 2025-11-07 中冶长天国际工程有限责任公司 一种制备类球形电池级四氧化三锰的方法

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US20130344332A1 (en) 2013-12-26

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